Methods of forming silicon oxides and methods of forming interlevel dielectrics

ABSTRACT

A method of forming silicon oxide includes depositing a silicon nitride-comprising material over a substrate. The silicon nitride-comprising material has an elevationally outermost silicon nitride-comprising surface. Such surface is treated with a fluid that is at least 99.5% H 2 O by volume. A polysilazane-comprising spin-on dielectric material is formed onto the H 2 O-treated silicon nitride-comprising surface. The polysilazane-comprising spin-on dielectric material is oxidized to form silicon oxide. Other implementations are contemplated.

TECHNICAL FIELD

Embodiments disclosed herein pertain to methods of forming silicon oxides and to methods of forming interlevel dielectrics.

BACKGROUND

In the fabrication of integrated circuitry, numerous devices are packed into small areas of a semiconductor substrate and interconnected to create an integrated circuit. Many of the individual devices are electrically isolated from one another. Accordingly, electrical isolation is an integral part of semiconductor device design for preventing unwanted electrical coupling between the adjacent components and devices. For example, interlayer/interlevel dielectric layers isolate structures from metal interconnect layers. Such may be required to fill very narrow gaps between adjacent structures, for example gaps which have high aspect ratios (ratio of depth to average width) where the features are also spaced close together. Insulative structures such as shallow trench isolation regions are also formed in recesses (trenches) within substrate material between components.

Common electrical isolation/insulative materials include doped and undoped silicon oxide-comprising materials. Silicon oxide-comprising dielectric materials may be deposited in a number of different manners, including chemical vapor deposition and plasma enhanced chemical vapor deposition. With the increase in aspect ratio between adjacent features, use of flowable materials such as spin-on dielectrics is increasing due to greater gap filling capability than from chemical vapor deposition methods. Such flowable processes include applying a liquid precursor solution of a silicon-containing polymer onto a spinning substrate. The substrate is then baked to remove solvent from the liquid, and thereby form an adhesive solid onto the substrate. Thereafter, the substrate is subjected to a thermal oxidizing ambient sufficient to oxidize the solid into the desired silicon oxide-comprising material.

One type of spin-on dielectric uses one or more polysilazanes as a starting precursor. Oxidation of polysilazane-containing spin-on dielectrics typically requires an underlying silicon dioxide layer deposited by decomposition of tetraethylorthosilicate (TEOS), particularly where such spin-on dielectrics are deposited into openings having high aspect ratios and closely spaced features (i.e., less than 75 nanometers. TEOS-deposited silicon dioxide facilitates oxidation of the lower/innermost portions of the polysilazane(s) within deep/high aspect ratio openings where the oxidizing ambient may not reach.

The TEOS-deposited silicon dioxide is typically deposited onto a silicon nitride layer which functions as a diffusion barrier. As spaced adjacent features continue to be moved closer together, it is becoming increasingly difficult to get both sufficiently thick TEOS-silicon dioxide layers and silicon nitride layers in between adjacent features to provide their respective functions. Elimination or thinning of the TEOS layer alone has been determined to provide inadequate complete oxidation of densified polysilazane-comprising spin-on dielectrics between very closely spaced adjacent features. Such can ultimately lead to shorts between contacts formed within openings of the resulting silicon oxide-comprising interlayer dielectrics. Accordingly, a need remains to address such issues.

While the invention was motivated from the above-identified challenges, the invention is in no way so limited in overcoming or addressing such challenges. Rather, the invention is only limited by the accompanying claims as literally worded and as appropriately interpreted in accordance with the doctrine of equivalents.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic sectional view of a substrate fragment in process in accordance with embodiments of the invention.

FIG. 2 is a view of the FIG. 1 substrate at a processing step subsequent to that shown by FIG. 1.

FIG. 3 is a view of the FIG. 2 substrate at a processing step subsequent to that shown by FIG. 2.

FIG. 4 is a view of the FIG. 3 substrate at a processing step subsequent to that shown by FIG. 3.

FIG. 5 is a view of the FIG. 4 substrate at a processing step subsequent to that shown by FIG. 4.

FIG. 6 is a diagrammatic sectional view of another substrate fragment in process in accordance with embodiments of the invention.

FIG. 7 is a diagrammatic sectional view of another substrate fragment in process in accordance with embodiments of the invention.

FIG. 8 is a view of the FIG. 7 substrate at a processing step subsequent to that shown by FIG. 7.

FIG. 9 is a view of the FIG. 8 substrate at a processing step subsequent to that shown by FIG. 8.

FIG. 10 is a view of the FIG. 9 substrate at a processing step subsequent to that shown by FIG. 9.

FIG. 11 is a view of the FIG. 10 substrate at a processing step subsequent to that shown by FIG. 10

FIG. 12 is a view of the FIG. 11 substrate at a processing step subsequent to that shown by FIG. 11.

FIG. 13 is a diagrammatic sectional view of another substrate fragment in process in accordance with embodiments of the invention.

FIG. 14 is a view of the FIG. 13 substrate at a processing step subsequent to that shown by FIG. 13.

FIG. 15 is a view of the FIG. 14 substrate at a processing step subsequent to that shown by FIG. 14.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS

Some embodiments of methods of forming silicon oxide in accordance with the invention are initially described with reference to FIGS. 1-5 with respect to a substrate fragment 10. Referring to FIG. 1, substrate fragment 10 comprises substrate material 12, and may comprise a semiconductor or other substrate. In the context of this document, the term “semiconductor substrate” or “semiconductive substrate” is defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure, including, but not limited to, the semiconductive substrates described above.

Example substrate 10 is shown as having a planar outermost surface, although such need not be so. Further although material 12 of substrate 10 may constitute a single homogenous composition, it may also comprise numerous layers and/or regions of integrated circuitry at various processing stages, and regardless, include multiple different composition materials and regions.

Referring to FIG. 2, a silicon nitride-comprising material 14 has been deposited over substrate 12. Such may be continuous, for example in the form of a blanketing layer as shown, or may be discontinuous. Such may be deposited by any existing or yet-to-be developed technique, and may be partially etched back or polished after deposition. Further, as examples, such may be lithographically or otherwise patterned, and/or comprise anisotropically etched spacers on sidewalls of other structures. Any selected thickness may be used. Regardless, silicon nitride-comprising material 14 may be considered as having an elevationally outermost silicon nitride-comprising surface 16 which may be continuous, discontinuous, planar and/or non-planar. Silicon nitride-comprising material 14 and surface 16 may or may not be stoichiometric silicon nitride (Si₃N₄).

Referring to FIG. 3, elevationally outermost silicon nitride-comprising surface 16 has been treated with a fluid that is at least 99.5% H₂O by volume. In one embodiment, the fluid is at least 99.9% H₂O by volume, and in one embodiment is at least 99.99% H₂O by volume. The fluid may be liquid, vapor, or a combination thereof. In one embodiment, the fluid is liquid deionized H₂O. In the context of this document, deionized H₂O includes any liquid H₂O that has been treated to remove minerals by one or more existing or yet-to-be developed deionization methods, and includes by distillation.

Where liquid treating is used, such might include one or a combination of immersing substrate 10 with surface 16 within a bath of the treating liquid and/or spraying surface 16 with the treating liquid. An example liquid temperature range is from 10° C. to 100° C. during the treating, with about room ambient temperature and a temperature of at least about 30° C. during the treating being specific examples. Pressure may be subatmospheric, room ambient, or greater than atmospheric during the treating. An example fluid temperature where the treating fluid is vapor is 100° C. and greater, with 125° C. being a specific example. Regardless, an example treating time with the fluid is from about 60 seconds to about 500 seconds. Substrate temperature during the treating may or may not be controlled, and may or may not be at room temperature. Regardless in one embodiment where the treating fluid comprises vapor, such may condense to liquid to be received onto elevationally outermost silicon nitride-comprising surface 16. In the context of this document, “onto” requires at least some direct physical touching contact of the two stated materials or layers.

Referring to FIG. 4, a polysilazane-comprising spin-on-dielectric material 18 has been formed onto H₂O-treated silicon nitride-comprising surface 16. Polysilazanes contain Si_(x)N_(y)H_(z)-type units in which the Si atoms are in a “reducing environment” in —Si—NH-bonds. Examples of suitable polysilazanes include hexamethyldisilazane, tetramethyldisilazane, octamethylcyclotetrasilazane, hexamethylcyclotrisilazane, diethylaminotrimethylsilazane, dimethyl-aminotrimethylsilazane, perhydro-polysilazane, including any mixtures of these or other polysilazanes. Spinfil polysilazane spin-on dielectric materials available from AZ Electronic Materials of Japan are specific examples. Material 18 may be provided to any suitable thickness and by any suitable liquid spin-on deposition technique.

In one embodiment, treating of an elevationally outermost silicon nitride-comprising surface with a fluid that is at least 99.5% H₂O by volume occurs in the spin-on-dielectric deposition chamber within which the polysilazane-comprising spin-on-dielectric material is deposited. In one embodiment, the substrate is not removed from the spin-on-dielectric deposition chamber between the treating with such fluid and the forming of the spin-on-dielectric thereon.

Referring to FIG. 5, polysilazane-comprising spin-on-dielectric material 18 (not shown) has been oxidized to form silicon oxide 20. Material 20 might include composition in addition to silicon oxide. Forming silicon oxide may include initially heating the substrate in the absence of an oxidizing ambient to remove organic solvent and produce a solid-phase polysilazane layer 18 (FIG. 4). For example, the initially deposited polysilazane material may be dried by baking on a hot plate at about 75° C. to about 350° C. for from about 1 to 5 minutes. The resultant layer may be subsequently subjected to wet or dry oxidation chemistries that will oxidize the polysilazane groups (Si_(x)N_(y)H_(z)) of the polysilazane material by replacing nitrogen and hydrogen atoms with oxygen atoms to form the layer into an oxygen rich material 20 (FIG. 5), i.e., a silicon oxide which may primarily be silicon dioxide. Example wet oxidation includes exposure to H₂O at a temperature of at least 600° C.

Some, all, or none of the H₂O may remain atop surface 16 at the time of depositing the polysilazane-comprising spin-on dielectric material, with none being shown as being left in FIG. 4. By way of example, some or all of remaining H₂O may be removed by exposure to isopropyl alcohol. Alternate drying techniques include spinning the substrate, exposure to reduced pressure/a vacuum, and air or other gas drying. FIG. 6 depicts an alternate embodiment substrate 10 a to that shown by FIG. 4 wherein some liquid H₂O 19 remains over surface 16 at the time of and upon depositing polysilazane-comprising spin-on dielectric material 18. Like numerals have been used with respect to the above-described embodiments, with differences being indicated with the suffix “a” or with different numerals. Accordingly in such embodiment, polysilazane-comprising material 18 deposits onto both H₂O 19 and silicon nitride-comprising surface 16. Liquid H₂O 19 onto which polysilazane-comprising spin-on dielectric material 18 is deposited may result from condensation of vapor H₂O.

Additional embodiment methods of forming silicon oxide, and for example forming an interlevel dielectric layer, are next-described with reference to FIGS. 7-12 with respect to a substrate fragment 10 b. Like numerals have been used with respect to the above-described embodiments, with differences being indicated with the suffix “b” or with different numerals. Referring to FIG. 7, raised features 26 have been formed over substrate 12. In one embodiment, raised features 26 comprise a plurality of upwardly projecting transistor gate structures. Transistor gate structures 26 are shown as comprising a gate dielectric 28, one or more conductive materials 30, an insulative cap 32, and anisotropically etched insulative sidewall spacers 34. Alternate transistor gate and/or other structures are also of course contemplated. Further and regardless, structures 26 need not be the same relative to one another.

In one embodiment in accordance with the tight spacing and high aspect ratio issues identified in the “Background” section above, raised features 26 are spaced from adjacent raised features by no greater than 75 nanometers, and wherein spaces between immediately adjacent raised features 26 have aspect ratios of at least 5:1. In one embodiment, line width of materials 28, 30 and 32 averages about 40 nanometers and space between adjacent spacers 34 averages about 40 nanometers. Example combined thickness of materials 28, 30, and 32 may be about 2,400 Angstroms, thereby providing an aspect ratio of about 6:1. Higher and lower aspect ratios are contemplated. Spacers 34 are shown as comprising laterally outer vertical sidewalls extending upwardly from material 12. Such may not so vertically extend, and may angle upwardly and laterally outward from material 12. Regardless, “aspect ratio” as used herein is with respect to height divided by average width.

Referring to FIG. 8, silicon nitride-comprising material 14 b has been deposited over the substrate having raised features 26. Silicon nitride-comprising material 14 b has a non-planar elevationally outermost silicon nitride-comprising surface 16 b, and less than fills space between adjacent of raised features 26.

Referring to FIG. 9, elevationally outermost silicon nitride-comprising surface 16 b above and between adjacent of raised features 26 is treated with a fluid that is at least 99.5% H₂O by volume. Any of the treatment techniques and fluids described above may be used.

Referring to FIG. 10, a polysilazane-comprising spin-on-dielectric material 18 b has been formed onto H₂O-treated silicon nitride-comprising surface 16 b. Such is oxidized to form silicon oxide 20 b, for example as shown in FIG. 11. Any of the processing as described above may be used.

Referring to FIG. 12, subsequent processing is depicted wherein contact openings 40 have been formed through silicon oxide 20 b and silicon nitride-comprising material 14 b to substrate material 12 therebeneath. One or more conductive materials 42 have been formed in contact openings 40. Conductive material 42 may comprise one or more of conductively doped semiconductive material (i.e., conductively doped polysilicon) or metal. Silicon oxide material 20 b may be deposited to a greater thickness than shown, followed by polish or etch back thereby forming an interlevel dielectric layer prior to etch and fill of contact openings 40 with conductive material 42.

The above processing enables elimination of deposition of a silicon dioxide layer by decomposition of tetraethylorthosilicate over silicon nitride-comprising material 14 b prior to deposition of polysilazane-comprising spin-on-dielectric material 18 b. Such may enable somewhat thicker deposition of a silicon nitride-comprising layer, for example to a thickness of at least 80 Angstroms for better oxidation barrier function in comparison with the typical prior art deposition thickness range of from 40 Angstroms to 70 Angstroms for features spaced about 40 nanometers apart. Prior art silicon dioxide layers for such spacing had thickness of from 100 Angstroms to 125 Angstroms. Accordingly, silicon oxide layer elimination may enable silicon nitride thicknesses on the order of 140 Angstroms to 195 Angstroms. Further and regardless, some, all, or none of the treating H₂O may remain over silicon nitride-comprising surface 16 b at the time of deposition of polysilazane-comprising spin-on-dielectric material 18 b.

Example methods of forming silicon oxide are next described with reference to FIGS. 13-15 with respect to a substrate fragment 75. Referring to FIG. 13, liquid H₂O 50 has been provided onto elevationally outermost silicon nitride-comprising surface 16 c. Such may be provided by one or both of direct exposure to liquid or by condensation from H₂O-containing vapor. In one embodiment, liquid H₂O 50 comprises at least 99.0% H₂O by volume. Higher concentration H₂O by volume is also contemplated, for example as described in any of the embodiments with respect to FIGS. 1-12. Polysilazane-comprising spin-on dielectric material would subsequently be formed onto the liquid H₂O and onto the silicon nitride-comprising surface. Such polysilazane-comprising spin-on-dielectric is ultimately oxidized to form silicon oxide. Any processing as described above may be used.

In one embodiment, the H₂O is removed from being received over tops of the raised features while leaving liquid H₂O contacting on portions of the silicon nitride-comprising surface between adjacent of the raised features, for example as shown in FIG. 14. Such may, for example be accomplished by exposing the FIG. 13 substrate to isopropyl alcohol, for example by a bath dip or spraying. Such may, by way of example only, be sufficient to remove H₂O liquid 50 from over tops of raised structures 26 but insufficient to remove liquid H₂O 50 received within deep narrow openings between raised structures 26. Regardless, one embodiment of the invention contemplates exposing the silicon nitride-comprising material to isopropyl alcohol before deposition of a polysilazane-comprising spin-on-dielectric material regardless of whether such removes some of the liquid H₂O. In one embodiment, exposure to isopropyl alcohol removes some and only some of the liquid H₂O from the silicon nitride-comprising surface. Alternate drying techniques include spinning, exposure to reduced pressure/a vacuum, and air or other gas drying.

Referring to FIG. 15, polysilazane-comprising spin-on-dielectric material 18 b has been deposited onto liquid H₂O 50 and onto silicon nitride-comprising surface 16 b. Such would be subsequently oxidized to form silicon oxide.

The embodiments of FIGS. 7-15 might form outermost surfaces of one or both of spacers 34 and caps 32 to comprise silicon nitride. If so, silicon nitride-comprising material 14 b might be eliminated, with processing otherwise occurring as indicated above, or otherwise. Such may be desirable for very high aspect ratio openings and very close spacing between immediately adjacent features 26 that may not provide sufficient open space for material 14 b.

In compliance with the statute, the subject matter disclosed herein has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the claims are not limited to the specific features shown and described, since the means herein disclosed comprise example embodiments. The claims are thus to be afforded full scope as literally worded, and to be appropriately interpreted in accordance with the doctrine of equivalents. 

1. A method of forming silicon oxide, comprising: depositing a silicon nitride-comprising material over a substrate, the silicon nitride-comprising material having an elevationally outermost silicon nitride-comprising surface; treating the elevationally outermost silicon nitride-comprising surface with a liquid that is at least 99.5% deionized H₂O by volume; forming a polysilazane-comprising spin-on dielectric material onto the deionized H₂O-treated silicon nitride-comprising surface; and oxidizing the polysilazane-comprising spin-on dielectric material to form silicon oxide.
 2. The method of claim 1 wherein the liquid is at least 99.9% deionized H₂O by volume.
 3. The method of claim 1 wherein the liquid is at least 99.99% deionized H₂O by volume.
 4. The method of claim 1 wherein the treating comprises immersing the silicon nitride-comprising surface within a bath of the liquid.
 5. The method of claim 1 wherein the treating comprises spraying the silicon nitride-comprising surface with the liquid.
 6. The method of claim 1 wherein the liquid is from 10° C. to 100° C. during the treating.
 7. The method of claim 6 wherein the liquid is at about ambient room temperature during the treating.
 8. The method of claim 6 wherein the liquid is at a temperature of at least about 30° C. during the treating.
 9. The method of claim 1 wherein the liquid is at ambient room pressure during the treating.
 10. The method of claim 1 wherein the treating is from about 60 seconds to about 500 seconds.
 11. A method of forming silicon oxide, comprising: depositing a silicon nitride-comprising material over a substrate, the silicon nitride-comprising material having an elevationally outermost silicon nitride-comprising surface; treating the elevationally outermost silicon nitride-comprising surface with a vapor that is at least 99.5% H₂O by volume; forming a polysilazane-comprising spin-on dielectric material onto the H₂O-treated silicon nitride-comprising surface; and oxidizing the polysilazane-comprising spin-on dielectric material to form silicon oxide.
 12. The method of claim 11 wherein the vapor is at least 99.9% H₂O by volume.
 13. The method of claim 11 wherein the vapor is at least 99.99% H₂O by volume.
 14. The method of claim 11 comprising condensing the vapor to liquid and onto the elevationally outermost silicon nitride-comprising surface.
 15. The method of claim 14 comprising forming the polysilazane-comprising spin-on dielectric material onto the condensed liquid.
 16. A method of forming silicon oxide, comprising: forming raised features over a substrate; depositing a silicon nitride-comprising material over the substrate having the raised features, the silicon nitride-comprising material having a non-planar elevationally outermost silicon nitride-comprising surface and less than filling space between adjacent of the raised features; providing liquid H₂O onto the elevationally outermost silicon nitride-comprising surface; forming a polysilazane-comprising spin-on dielectric material onto the liquid H₂O and onto the silicon nitride-comprising surface; and oxidizing the polysilazane-comprising spin-on dielectric material to form silicon oxide.
 17. The method of claim 16 comprising exposing the silicon nitride-comprising material to isopropyl alcohol after the providing and before the forming.
 18. The method of claim 17 wherein the exposing removes some and only some of the liquid H₂O from the silicon nitride-comprising surface.
 19. The method of claim 16 comprising, after the providing and before the forming, removing the liquid H₂O from being received over tops of the raised features while leaving liquid H₂O contacting on portions of the silicon nitride-comprising surface between adjacent of the raised features, the polysilazane-comprising spin-on dielectric material being formed onto said portions.
 20. The method of claim 19 wherein the removing comprises exposure to isopropyl alcohol.
 21. The method of claim 16 wherein the liquid H₂O comprises at least 99.0% H₂O by volume.
 22. The method of claim 16 wherein the liquid H₂O comprises at least 99.5% H₂O by volume.
 23. The method of claim 16 wherein the liquid H₂O comprises at least 99.99% H₂O by volume.
 24. The method of claim 16, being void of depositing a silicon dioxide layer by decomposition of tetraethylorthosilicate between the forming of the raised features and the depositing of the silicon nitride-comprising material; wherein the raised features are spaced from adjacent raised features by no greater than 75 nanometers; wherein spaces between the raised features have aspect ratio of at least 5:1; and wherein the deposited silicon nitride-comprising material is a layer having a thickness of at least 80 Angstroms.
 25. A method of forming an interlevel dielectric layer comprising silicon oxide in the fabrication of integrated circuitry, comprising: forming a plurality of upwardly projecting transistor gate structures over a substrate; depositing a silicon nitride-comprising material over and between the upwardly projecting transistor gate structures, the silicon nitride-comprising material having a nonplanar elevationally outermost silicon nitride-comprising surface and less than filling space between adjacent of the upwardly projecting transistor gate structures; treating the elevationally outermost silicon nitride-comprising surface above and between adjacent of the upwardly projecting transistor gate structures with a fluid that is at least 99.5% H₂O by volume; forming a polysilazane-comprising spin-on dielectric material onto the H₂O-treated silicon nitride-comprising surface; and oxidizing the polysilazane-comprising spin-on dielectric material to form silicon oxide.
 26. The method of claim 25 wherein the fluid comprises liquid.
 27. The method of claim 26 comprising forming the polysilazane-comprising spin-on dielectric material onto the liquid.
 28. The method of claim 25 wherein the fluid comprises vapor.
 29. The method of claim 28 comprising condensing the vapor to liquid and onto the elevationally outermost silicon nitride-comprising surface.
 30. The method of claim 29 comprising forming the polysilazane-comprising spin-on dielectric material onto the condensed liquid.
 31. The method of claim 25 wherein the fluid comprises at least 99.9% H₂O by volume.
 32. The method of claim 25 wherein the fluid comprises at least 99.99% H₂O by volume.
 33. The method of claim 25 being void of depositing a silicon dioxide layer by decomposition of tetraethylorthosilicate between the forming of the transistor gate structures and the depositing of the silicon nitride-comprising material.
 34. A method of forming silicon oxide, comprising: depositing a silicon nitride-comprising material over a substrate, the silicon nitride-comprising material having an elevationally outermost silicon nitride-comprising surface; providing the substrate with silicon nitride-comprising material within a spin-on dielectric deposition chamber; within the spin-on dielectric deposition chamber, treating the elevationally outermost silicon nitride-comprising surface with a fluid that is at least 99.5% H₂O by volume; within the spin-on dielectric deposition chamber, forming a polysilazane-comprising spin-on dielectric material onto the H₂O-treated silicon nitride-comprising surface; and oxidizing the polysilazane-comprising spin-on dielectric material to form silicon oxide.
 35. The method of claim 34 wherein the substrate is not removed from the spin-on dielectric deposition chamber between the treating and the forming.
 36. A method of forming silicon oxide, comprising: depositing a silicon nitride-comprising material over a substrate, the silicon nitride-comprising material having an elevationally outermost silicon nitride-comprising surface; treating the elevationally outermost silicon nitride-comprising surface with a fluid that is at least 99.5% deionized H₂O by volume; forming a polysilazane-comprising spin-on dielectric material onto the deionized H₂O-treated silicon nitride-comprising surface; and oxidizing the polysilazane-comprising spin-on dielectric material to form silicon oxide. 